Thermo-physical and thermal cycling properties of plasma-sprayed BaLa2Ti3O10 coating as potential thermal barrier materials

Increased turbine inlet temperature in advanced turbines has promoted the development of thermal barrier coating (TBC) materials with high-temperature capability. In this paper, BaLa₂Ti₃O₁₀ (BLT) was produced by solid-state reaction of BaCO₃, TiO₂ and La₂O₃ at 1500 °C for 48 h. BLT showed phase stability between room temperature and 1400 °C. BLT revealed a linearly increasing thermal expansion coefficient with increasing temperature up to 1200 °C and the coefficients of thermal expansion (CTEs) are in the range of 1 × 10^− 5–12.5 × 10^− 6 K^− 1, which are comparable to those of 7YSZ. BLT coatings with stoichiometric composition were produced by atmospheric plasma spraying. The coating contained segmentation cracks and had a porosity of around 13%. The microhardness for the BLT coating is 3.9–4.5 GPa. The thermo-physical properties of the sprayed coating were investigated. The thermal conductivity at 1200 °C is about 0.7 W/mK, exhibiting a very promising potential in improving the thermal insulation property of TBC. Thermal cycling result showed that the BLT TBC had a lifetime of more than 1100 cycles of about 200 h at 1100 °C. The failure of the coating occurred by cracking at the thermally grown oxide (TGO) layer due to severe oxidation of bond coat. Based on the above merits, BLT could be considered as a promising material for TBC applications.     

一种新型经济高效非晶涂层的制备与性能表征

利用火焰喷涂技术喷涂自制的气雾化合金粉末取代非晶粉末,制备了NiFeBSiNb非晶纳米晶涂层。分别对粉末和涂层的微观组织结构和热力学性能进行了表征。结果表明,自制的合金粉末球形度较好,大多为球形或椭球形;主要为晶体结构,由Nb₂Ni₂₁B₆晶体相和(Ni,Fe)₂₃B₆固溶体组成。而经过火焰喷涂制备的涂层,形成了非晶相和纳米晶相。通过公式计算此合金体系粉末和涂层形成非晶相的临界冷却速率分别为6.01×10₅K/s和4.56×10₃K/s,解释了在粉末制备过程中较难形成非晶相而喷涂过程中形成非晶结构比较容易。对涂层的摩擦磨损性能进行了测试,涂层摩擦系数仅为0.17,具有优异的耐磨性能。     

Synthesis of ultrafine (Ti, W, Mo, V)(C, N)–Ni composite powders by low-energy milling and subsequent carbothermal reduction–nitridation reaction

Ultrafine (Ti, W, Mo, V)(C, N)–Ni composite powders with globular-like particles of 50–300 nm were synthesized at static nitrogen pressure from oxides by a simple and cost-effective route which combines traditional low-energy milling plus carbothermal reduction–nitridation (CRN) techniques. Reaction path of the (Ti, W, Mo, V)(C, N)–Ni system was discussed by X-ray diffraction (XRD) and thermogravimetry–differential scanning calorimetry (TG–DSC), and microstructure of the milled powders and final products was studied by scanning electron microscopy (SEM) and transmission electron microscope (TEM), respectively. The results show that CRN reaction has been enhanced by nano-TiO₂ and nano-carbon powders. Thus, the preparation of (Ti, 15W, 5Mo, 0.2V)(C, N)–20Ni is at only 1300 °C for 1 h. During synthesizing reaction, Ni solid solution phase forms at about 700 °C and reduction–carbonization of WO₂ and MoO₂ occurs below 900 °C. The reactions of TiO₂ → Ti₃O₅, Ti₃O₅ → Ti(C, O) and Ti(C, O) → Ti(C, N) take place at about 930 °C, 1203 °C and 1244 °C, respectively.     

A convenient thermal reduction–nitridation route to nanocrystalline molybdenum nitride (Mo2N)

Nanocrystalline molybdenum nitride (γ-Mo₂N) was synthesized via a thermal reduction–nitridation route by the reaction of metallic sodium with anhydrous molybdenum pentachloride and ammonium chloride in an autoclave at 550 °C. X-ray powder diffraction pattern indicated that the product was cubic Mo₂N, and the cell constant was a = 4.161 Å. Scanning electron microscopy image showed that it consisted of particles with an average size of about 30 nm. The product was also studied by BET and TGA. It had good thermal stability and oxidation resistance below 400 °C in air.     

Correlation of crystallization behavior and mechanical properties of thermal sprayed PEEK coating

An amorphous PEEK coating was prepared on an Al substrate by a flame spraying process. The amorphous coating was subjected to an annealing treatment under an annealing temperature from 180 to 300 °C and a holding time from 1 to 30 min. The cold crystallization behavior of the as-sprayed coating differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WAXD) measurements. The hardness and tribological behavior of the coatings were investigated. Both DSC and WAXD analysis revealed that the annealed coatings exhibited a semi-crystalline structure. Coexistence of double crystal entities in annealed coatings was deduced. The annealed coatings exhibit higher hardness, lower friction coefficient and wear rate. Both the annealing temperature and holding time can benefit the coating hardness. The annealing condition in the studied range has little influence on the tribological behavior of the coatings. The variances of the coating mechanical properties were correlated with the modifications of the coating structures induced by the annealing treatments.     

Microstructure and thermal cycle resistance of plasma sprayed mullite coatings made from secondary mullitized natural andalusite powder

Natural andalusite powder was calcinated at a high temperature in air to realize secondary mullitization. The resultant secondary mullitized powder was spray-dried and heat-treated to improve sprayable capability. The heat-treated spherical powder was then plasma sprayed onto Ni-based high-temperature alloy (Hastelloy C-276) to form mullite coatings. The chemical composition and phase structure of the as-sprayed and thermally cycled mullite coatings were determined by means of energy dispersive X-ray fluorescence (ED-XRF) and X-ray diffraction. The microstructure of the as-sprayed coatings was analyzed by using a scanning electron microscope; and their porosity, microhardness and bonding strength were measured. Moreover, the phase transition temperature and enthalpy of the coatings were determined by means of differential scanning calorimetry; and their thermal shock resistance was evaluated as well. Results show that the spray-dried and heat-treated powder consists of mullite and a small amount of Al₂O₃; while the as-sprayed mullite coatings are composed of crystalline mullite as the major phase and a small amount of amorphous glass phase. During thermal cycle test, the amorphous glass phase is partially transformed to crystalline mullite, finally leading to failure of the coatings. Whether before or after thermal cycle, the mullite coatings experience phase transition around 980 °C, and the enthalpy of crystallization is determined to be − 141.9 × 10^− 3 J/kg and − 95.48 × 10^− 3 J/kg, respectively. The as-sprayed mullite coatings have a porosity of about 6.0 ± 0.2% and possess good thermal cycle resistance, showing promising prospect in a high-temperature application.     

Hydriding/dehydriding behavior of Mg2CoH5 produced by reactive mechanical milling

Complex Mg₂CoH₅ hydride was obtained by a combined procedure that included a milling stage of a 2Mg–Co mixture under argon followed by reactive mechanical alloying (RMA) under hydrogen, both at room temperature. During RMA, MgH₂ is produced at short milling times (10 h) and Mg₂CoH₅ (50 wt%) after 90 h. Improvement in the yield and the formation times could be associated with both refinement of microstructure and enhancement of intermixing of Mg–Co during pre-milling stage. DSC studies of Mg₂CoH₅ phase produced by RMA show that the starting decomposition temperature is about 205 °C.Absorption and desorption PCIs were determined under static (300 °C) and dynamic (230–330 °C) conditions. An important hysteresis and two plateaus were observed and correlated with formation/decomposition of Mg₂CoH₅ (high-pressure plateau) and Mg₆Co₂H₁₁ (low-pressure plateau) hydrides. For comparing hydrogen sorption kinetics, Mg₂CoH₅ (65 wt%) was also obtained by a sintering method at 410 °C and 6.0 MPa of hydrogen pressure. Absorption was very fast in the temperature range of 150–350 °C, independently of synthesis procedure. However, desorption curves showed a better behavior for RMA powders.MgCo was observed after decomposition of Mg₂CoH₅ under particular thermal treatments, while MgCo₂ phase was not detected. The results of this study reinforce the idea that kinetics factors related with atomic mobility play a key role in the formation of Mg–Co intermetallics.     

Nanocrystalline NiAl Coating Prepared by HVOF Thermal Spraying

Nanocrystalline NiAl intermetallic powder was prepared by mechanical alloying (MA) of Ni₅₀Al₅₀ powder mixture and then deposited on low carbon steel substrates by high velocity oxy fuel (HVOF) thermal spray technique using two sets of spraying parameters. X-ray diffraction (XRD), scanning electron microscopy (SEM), transition electron microscopy (TEM), differential scanning calorimetry (DSC), and hardness test were used to characterize the prepared powders and coatings. The MA of Ni₅₀Al₅₀ powder mixture led to the formation of NiAl intermetallic compound. The resulting powder particles were three dimensional in nature with irregular morphology and a crystallite size of ~10 nm. This powder was thermally sprayed by HVOF technique to produce coating. The deposited coating had a nanocrystalline structure with low oxide and porosity contents. The hardness of coatings was in the range of 5.40-6.08 GPa, which is higher than that obtained for NiAl coating deposited using conventional powders.     

The Effect of Heat Treatment on the Oxidation Behavior of HVOF and VPS CoNiCrAlY Coatings

Free-standing VPS and HVOF CoNiCrAlY coatings were produced. The as-sprayed HVOF coating retained the γ/β microstructure of the feedstock powder, and the VPS coating consisted of a single (γ) phase. A 3-h, 1100 °C heat treatment in vacuum converted the single-phase VPS coating to a two-phase γ/β microstructure and coarsened the γ/β microstructure of the HVOF coating. Oxidation of free-standing as-sprayed and heat-treated coatings of each type was carried out in air at 1100 °C for a duration of 100 h. Parabolic rate constant(s), K _p, were determined for free-standing, as-sprayed VPS and HVOF coatings as well as for free-standing coatings that were heat treated prior to oxidation. The observed increase in K _p following heat treatment is attributed to a sintering effect eliminating porosity from the coating during heat treatment. The lower K _p values determined for both HVOF coatings compared to the VPS coatings is attributed to the presence of oxides in the HVOF coatings, which act as the barrier to diffusion. Oxidation of the as-sprayed coatings produced a dual-layer oxide consisting of an inner α-Al₂O₃ layer and outer spinel layer. Oxidation of the heat-treated samples resulted in a single-layer oxide, α-Al₂O₃. The formation of a thin α-Al₂O₃ layer during heat treatment appeared to prevent nucleation and growth of spinel oxides during subsequent oxidation.     

Microstructure of Suspension Plasma Spray and Air Plasma Spray Al2O3-ZrO2 Composite Coatings

Al₂O₃-ZrO₂ coatings were deposited by the suspension plasma spray (SPS) molecularly mixed amorphous powder and the conventional air plasma spray (APS) Al₂O₃-ZrO₂ crystalline powder. The amorphous powder was produced by heat treatment of molecularly mixed chemical solution precursors below their crystallization temperatures. Phase composition and microstructure of the as-synthesized and heat-treated SPS and APS coatings were characterized by XRD and SEM. XRD analysis shows that the as-sprayed SPS coating is composed of α-Al₂O₃ and tetragonal ZrO₂ phases, while the as-sprayed APS coating consists of tetragonal ZrO₂, α-Al₂O₃, and γ-Al₂O₃ phases. Microstructure characterization revealed that the Al₂O₃ and ZrO₂ phase distribution in SPS coatings is much more homogeneous than that of APS coatings.     

Thermal behavior of the amorphous precursors of the ZrO2–GaO1.5 system

The amorphous precursors of the ZrO₂–GaO_1.5 system on the ZrO₂-rich side of the concentration range were prepared by co-precipitation from aqueous solutions of the corresponding salts. Thermal behavior of the amorphous precursors was monitored using differential thermal analysis (DTA), X-ray powder diffraction (XRD), Raman spectroscopy and field emission scanning electron microscopy (FE-SEM). Crystallization temperature of the amorphous precursors rose with an increase in the GaO_1.5 content, from 405 °C (0 mol% GaO_1.5) to 720 °C (50 mol% GaO_1.5). The results of Rietveld refinements indicated that the maximum solubility of Ga³⁺ ions in the ZrO₂ lattice (43 mol%) occurred in the metastable products obtained after crystallization of the amorphous precursors. Further thermal treatment caused a decrease of the solubility limits, which became negligible after calcination at 1100 °C. The results of Raman spectroscopy showed that the incorporation of Ga³⁺ ions partially stabilized the tetragonal polymorph of ZrO₂, but could not stabilize its cubic polymorph. The incorporation of Ga³⁺ ions caused a linear decrease in the unit-cell volume of the ZrO₂-type solid solutions, but the rate of the decrease turned out to be smaller than the rate obtained after the incorporation of bigger Fe³⁺ ions.     

Effect of sintering on microstructure and mechanical properties of nano-TiO2 dispersed Al65Cu20Ti15 amorphous/nanocrystalline matrix composite

Mechanically alloyed Al₆₅Cu₂₀Ti₁₅ amorphous alloy powder with or without 10 wt% nano-TiO₂ dispersion was consolidated by isothermal spark plasma sintering in the range 200–500 °C with pressure up to 50 MPa. Selected samples were separately cold compacted with 50 MPa pressure and sintered at 500 °C using controlled atmosphere resistance and microwave heating furnaces. Phase and microstructural evolution at appropriate stages of mechanical alloying/blending and sintering was monitored by X-ray diffraction and scanning and transmission electron microscopy. Measurement and comparison of relevant properties (density/porosity, microhardness and yield strength) of the sintered compacts suggest that spark plasma sintering is the most appropriate technique for developing nano-TiO₂ dispersed amorphous/nanocrystalline Al₆₅Cu₂₀Ti₁₅ matrix composite for structural application.     

Corrosion and wear behavior of thermally sprayed nano ceramic coatings on commercially pure Titanium and Ti–13Nb–13Zr substrates

Surface treatments and coatings are the practical approaches used to extend the lifetime of components and structures especially when the surface is the most solicited part of the considered engineering component. Hard thermally sprayed coating is one of the most wear resistance coating widely used in many practical mechanical applications. In the construction of articulating parts of medical devices, titanium and its alloys have to be surface coated to improve their tribocorrosion behavior. In this way, the use of porous thermal coatings is known to be a strategy for better binding bone or tissue on femoral stem for example. It is, thus, important to evaluate the corrosion and the wear behaviors of such materials for biosecurity considerations in the human body. In this study, we investigate the behavior of new nano ZrO₂ and Al₂O₃-13 wt.% TiO₂ thermal sprayed coatings on commercially pure (cp)-Ti (grade 4) and titanium alloy substrates. Friction and wear tests against Al₂O₃ balls showed that the wear resistance of Al₂O₃-13 wt.% TiO₂ is better than that ZrO₂ coating. Both plasma sprayings have similar abrasive wear behavior; however, the average friction coefficient is higher for alumina–titania coating. Electrochemical tests, open circuit potential monitoring and potentiodynamic polarization, were performed in simulated body conditions (Hank’s solution, 37 °C). Results showed that corrosion resistance was appreciably higher for alumina–titania coating.     

Amorphous and nanocrystalline sputtered Mg–Cu thin films

Binary Mg–Cu amorphous alloys were first fabricated in 1980s via liquid quenching. In this study, the Mg_1−xCu_x (x varying from 38 at.% to 82 at.%) partially amorphous thin films are prepared via co-sputtering. Upon thermal annealing, the Mg₂Cu or MgCu₂ nanocrystalline phases are induced in the Mg-rich or Cu-rich thin films, respectively. Due to the presence of fine nanocrystalline Mg₂Cu or MgCu₂ particles in the Mg–Cu amorphous matrix, the as-sputtered thin films show satisfactory Young's modulus 100 GPa and hardness 4 GPa.     

Nano-phenomena during exposure of plasma-sprayed ceria stabilised zirconia coatings to oxygen rich environments

Plasma-sprayed zirconia coatings are widely used for oxidation protection. Up-to-date, microstructural stabilisation of such coatings is mainly achieved with yttrium oxide; however recent scientific attempts indicated that ceria stabilised zirconia coatings could be a very promising alternative. In the present work, a coating of this kind has been deposited onto a Ni-based superalloy with the interference of a NiCrAlY bond coating by plasma spraying. Its oxidation resistance was estimated with thermogravimetric analysis with exposure at 1100 °C in air. The microstructure of the as-sprayed coating was studied with X-ray diffraction and electron microscopy before and after oxidation. From this examination it was deduced that ceria stabilised zirconia (CSZ) coating is rather stable at the temperature under question. However reduction of ceria takes place at larger exposure periods.     

Characterization of plasma sprayed Fe-17Cr-38Mo-4C amorphous coatings crystallizing at extremely high temperature

A Fe-17Cr-38Mo-4C alloy powder was plasma sprayed by three processes: an 80 kW low-pressure plasma spray (LPPS), a 250 kW high-energy plasma spray (HPS), and a 40 kW conventional plasma spray (APS). The as-sprayed coating obtained by the LPPS process is composed of only amorphous phase. As-sprayed coatings obtained by the HPS and APS processes are a mixture of amorphous and crystalline phases. The three as-sprayed coatings exhibit a high hardness of 1000 to 1100 DPN. The amorphous phase in these coatings crystallizes at a high temperature of about 920 K. A very fine structure composed of hard ϰ-phase and carbides is formed after crystallization. The hardness of the coating obtained by LPPS reaches a maximum of 1450 DPN just after crystallization on tempering and retains a high hardness more than 1300 DPN after tempering at high temperatures of 1173 or 1273 K. The corrosion potential of the amorphous coating is the highest among the three coatings and higher than that of a SUS316L stainless steel coating. The anodic polarization measurements infer that the corrosion resistance of the amorphous coating is superior or comparable to SUS316L stainless steel coating in H₂SO₄ solution.     

Wear-resistant Ti–B–N nanocomposite coatings synthesized by reactive cathodic arc evaporation

Wear-resistant Ti–B–N coatings have been synthesized by reactive arc evaporation of Ti–TiB₂ compound cathodes in a commercial Oerlikon Balzers Rapid Coating System. Owing to the strong non-equilibrium conditions of the deposition method, a TiN–TiB_x phase mixture is observed at low N₂ partial pressures, as determined by elastic recoil detection analysis, X-ray diffraction, X-ray spectroscopy, transmission electron microscopy and selected area electron diffraction. The indicated formation of a metastable solid solution of B in face-centered cubic TiN gives rise to a maximum in hardness (>40 GPa) and wear resistance on the expense of increased compressive stresses. A further saturation of the nitrogen content results in the formation of a TiN–BN nanocomposite, where the BN phase fraction was tailored by the target composition (Ti/B ratio of 5/3 and 5/1). However, the amorphous nature of the BN phase does not support self-lubricious properties, showing friction coefficients of 0.7 ± 0.1 against alumina. The effect of an increased bias voltage on structure and morphology was investigated from −20 to −140 V and the thermal stability assessed in Ar and air by simultaneous thermal analysis up to 1400 °C.     

Dominant microstructural feature over photocatalytic activity of high velocity oxy-fuel sprayed TiO2 coating

TiO₂ photocatalytic coatings were deposited through high velocity oxy-fuel spray using anatase powder and rutile powder as feedstock. The as-sprayed TiO₂ coating was composed of anatase phase and rutile phase. The anatase content in the coating was significantly influenced by fuel gas flow and melting condition of spray powder. A high anatase content of 35% was achieved for the coating deposited using rutile powder. The anatase content in the coating deposited using anatase powder reached 55-65%. The as-sprayed TiO₂ coating was photocatalytically reactive for degradation of acetaldehyde in air. The photocatalytic activity was influenced by spray conditions. The surface morphology and phase structure of coatings deposited at different spray conditions were investigated to clarify the relationship between the coating microstructure and activity. It is found that the photocatalytic activity is significantly influenced by anatase content and surface area.     

Metal dusting resistant alumina forming coatings for syngas production

Metal dusting corrosion of NiCrAl(Y)-based alumina forming coatings has been simulated in carbon-supersaturated environments (CO–H₂) at 650 °C. Atmospheric plasma spray (APS) and powder plasma welding (PPW) methods have been employed to deposit alumina forming coatings on Inconel 601 substrate alloy surfaces. Since most currently available high temperature alloys are prone to metal dusting, understanding and thereby controlling metal dusting corrosion is key to many operations and developments related to syngas production. The focus of this research is to evaluate the performance of alumina forming coatings under laboratory conditions. In addition to the effect of coating chemistry and microstructure (based on method of application) on the corrosion process, the mechanistic aspects of metal dusting are discussed with particular attention to the stages of microstructure evolution as degradation proceeds.     

Characterization of the corrosion products of electrodeposited Zn, Zn–Co and Zn–Mn alloys coatings

The morphology, composition, phase composition and corrosion products of coatings of pure Zn (obtained from two types of electrolytic bath: an acidic bath (Zn_acid) and a cyanide-free alkaline bath (Zn_alkaline)) and of Zn–Mn and Zn–Co alloys on steel substrates were studied. To achieve this, diverse techniques were used, including polarization curves, atomic force microscopy (AFM), scanning electron microscopy (SEM), glow discharge spectroscopy (GDS), X-ray diffraction (XRD), and the salt spray test. In the salt spray test, the exposure time required for the coatings to exhibit red corrosion (associated with the oxidation of steel) decreased in the following order: Zn–Mn_(432h) > Zn–Co_(429h) > Zn_{alkaline(298h)} > Zn_acid(216h). The shorter exposure times required for corrosion of the pure Zn coatings are related to the coating composition and the crystallographic structure. Analysis of the corrosion products disclosed that Zn₅(OH)₈Cl₂·H₂O was a corrosion product of all of the coatings tested. However, the formation of oxides of manganese (MnO, Mn_0.98O₂, Mn₅O₈) in the Zn–Mn coating, and the formation of the hydroxide Zn₂Co₃(OH)₁₀·2H₂O in the Zn–Co coating, produced more compact and stable passive layers, with lower dissolution rates.